EP0885256A1 - Urethanschaum für schuhsolen - Google Patents
Urethanschaum für schuhsolenInfo
- Publication number
- EP0885256A1 EP0885256A1 EP19970905431 EP97905431A EP0885256A1 EP 0885256 A1 EP0885256 A1 EP 0885256A1 EP 19970905431 EP19970905431 EP 19970905431 EP 97905431 A EP97905431 A EP 97905431A EP 0885256 A1 EP0885256 A1 EP 0885256A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- foam
- mean
- density
- urethane foam
- cell diameter
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000006260 foam Substances 0.000 title claims abstract description 115
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 210000004027 cell Anatomy 0.000 claims abstract description 35
- 210000003491 skin Anatomy 0.000 claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 239000003381 stabilizer Substances 0.000 claims abstract description 14
- 210000004927 skin cell Anatomy 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 9
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 5
- 229920005830 Polyurethane Foam Polymers 0.000 description 18
- 239000011496 polyurethane foam Substances 0.000 description 18
- -1 polydimethylsiloxanes Polymers 0.000 description 13
- 229920005862 polyol Polymers 0.000 description 11
- 150000003077 polyols Chemical class 0.000 description 11
- 229920001577 copolymer Polymers 0.000 description 10
- 238000000465 moulding Methods 0.000 description 10
- 239000004872 foam stabilizing agent Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 239000004721 Polyphenylene oxide Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 229920000570 polyether Polymers 0.000 description 7
- 239000004604 Blowing Agent Substances 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 229920005906 polyester polyol Polymers 0.000 description 6
- 229920001296 polysiloxane Polymers 0.000 description 6
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 5
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920005903 polyol mixture Polymers 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 125000005702 oxyalkylene group Chemical group 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920001921 poly-methyl-phenyl-siloxane Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- ZWVMLYRJXORSEP-UHFFFAOYSA-N 1,2,6-Hexanetriol Chemical compound OCCCCC(O)CO ZWVMLYRJXORSEP-UHFFFAOYSA-N 0.000 description 1
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical class C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- ICLCCFKUSALICQ-UHFFFAOYSA-N 1-isocyanato-4-(4-isocyanato-3-methylphenyl)-2-methylbenzene Chemical compound C1=C(N=C=O)C(C)=CC(C=2C=C(C)C(N=C=O)=CC=2)=C1 ICLCCFKUSALICQ-UHFFFAOYSA-N 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- DJRMKXPWIGWFFL-UHFFFAOYSA-N ethane-1,2-diol;hexanedioic acid;2-(2-hydroxyethoxy)ethanol Chemical compound OCCO.OCCOCCO.OC(=O)CCCCC(O)=O DJRMKXPWIGWFFL-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- SNVLJLYUUXKWOJ-UHFFFAOYSA-N methylidenecarbene Chemical compound C=[C] SNVLJLYUUXKWOJ-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000000963 oxybis(methylene) group Chemical group [H]C([H])(*)OC([H])([H])* 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
- C08G18/4247—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids
- C08G18/425—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids the polyols containing one or two ether groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0008—Foam properties flexible
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0033—Foam properties having integral skins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0041—Foam properties having specified density
- C08G2110/0058—≥50 and <150kg/m3
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0041—Foam properties having specified density
- C08G2110/0066—≥ 150kg/m3
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2410/00—Soles
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
- Y10T428/2495—Thickness [relative or absolute]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
- Y10T428/24992—Density or compression of components
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249981—Plural void-containing components
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249987—With nonvoid component of specified composition
- Y10T428/249988—Of about the same composition as, and adjacent to, the void-containing component
- Y10T428/249989—Integrally formed skin
Definitions
- the present invention relates to a urethane foam for shoe soles where the sizes of the skin and core cells are markedly different.
- a polyurethane foam is prepared by mixing and stirring a polyisocyanate and a polyol mixture comprising a polyol, a catalyst, a blowing agent, a foam stabilizer (a surfactant), and other optional auxiliaries, and thereby allowing the components to react.
- Shoe soles made of polyurethane foam exhibit excellent properties such as lightness, impact resistance, chemical resistance, abrasion resistance, and bending resistance. With respect to midsoles, in particular, there has recently been a rapid trend toward density reduction for the purposes of reduction in cost and weight. Density reduction in a water-blown polyurethane foam for shoe soles is normally achieved by increasing the relative amount of water in the polyol mixture to increase the generation of CO 2 gas for foaming.
- an integral skin foam method is used to mold automobile interiors without affecting the foam's mechanical properties. It is characterized in that the skin layer and inner foam are simultaneously molded. This can be achieved by suppressing the expansion of the skin portion which comes into contact with the mold's inner wall during the reaction.
- the skin layer is a high-density elastomer, reducing the molded density of the foam as a whole is limited. Also, a chlorofluorocarbon-type blowing agent is required for the integral skin method, which causes various problems in a process where water is used as a blowing agent.
- the present invention is to solve the above problems. Accordingly, the present invention is to provide a polyurethane foam possessing excellent moldability which maintains a high split tear strength even when the relative amount of water is increased to reduce the molded density of the polyurethane foam.
- the present invention is directed to a urethane foam for shoe soles prepared by reacting a compound having at least two isocyanate-reactive hydrogen atoms and a molecular weight of 400 to 10000 with a polyisocyanate in the presence of a foam stabilizer, water and a catalyst, characterized in that the ratio r 1 /r 2 of a mean skin cell diameter r 1 to a mean core cell diameter r 2 is 0.02 to 0.80, wherein the mean skin cell diameter r 1 is defined as the mean diameter of the cells which form the skin portion of a urethane foam extending from the surface to a depth of 5% of the foam thickness and the mean core cell diameter r 2 is defined as the mean diameter of the cells which form the core portion of a urethane foam extending from a depth of 40% to a depth of 60% of the foam thickness;
- BRIEF DESCRIPTION OF THE DRAWING Figure 1 is a perspective of a polyurethane foam test piece for the determination of split tear value.
- an isocyanate-reactive compound 400 to 10000 (hereinafter referred to as "an isocyanate-reactive compound”) and a polyisocyanate in the presence of a foam stabilizer, water and a catalyst, wherein the ratio r 1 /r 2 of the mean skin cell diameter r 1 to the mean core cell diameter r 2 is 0.02 to 0.80, preferably 0.02 to 0.60, more preferably 0.02 to 0.40, and still more preferably 0.03 to 0.30.
- the mean skin cell diameter r 1 is defined as the mean diameter of the cells which form the skin portion of a urethane foam extending from the surface to a depth of 5% of the foam thickness.
- the mean core cell diameter r 2 is defined as the mean diameter of the cells which form the core portion of a urethane foam
- r 1 is obtained with the cells which form the portion of the urethane foam extending from the surface to a depth of 0.5 mm
- r 2 is obtained with the cells which form the portion extending from a depth of 4 mm to a depth of 6 mm of the foam sheet.
- the mean cell diameters r 1 and r 2 are obtained by taking a cross-sectional photomicrograph of the urethane foam using a scanning electron microscope (SEM), and calculating number (arithmetic) average of the maximum diameters in a given direction (also referred to as Krummbein diameter as described in "Silikattechik” 20 (6) 189-192 (1969) ).
- the ratio of the mean skin cell diameter r 1 to the mean core cell diameter r 2 (r 1 /r 2 ) is less than 0.02, cushion quality, an essential property of foams, may be impaired. When the ratio exceeds 0.80, the foam surface's cosmetic appearance and moldability may be impaired.
- the mean skin cell diameter ( r 1 ) is not more than 0.20 mm, preferably 0.03 to 0.20 mm, more preferably 0.03 to 0.16 mm, particularly preferably 0.03 to 0.12 mm. Also, the mean core cell diameter (r 2 ) is
- r 1 preferably 0.25 to 1.20 mm, more preferably 0.30 to 1.00 mm, still more preferably 0.35 to 0.90 mm.
- mean skin cell diameter r 1 exceeds 0.20 mm, smoothness of the foam surface may be impaired.
- mean core cell diameter r 2 is less than 0.25 mm, it tends to become difficult to improve the split tear strength.
- r 2 exceeds 1.20 mm, void may occur, thereby impairing the product quality.
- r 1 /r 2 is 0.02 to 0.60, wherein r 2 is 0.25 to 1.20 mm; a more preferred embodiment is that r 1 /r 2 is 0.02 to 0.60, wherein r 2 is 0.30 to 1.00 mm ; and a still more preferred embodiment is that r 1 /r 2 is 0.02 to 0.40, wherein r 2 is 0.30 to 1.00 mm. In a still more preferable embodiment, r 1 /r 2 is 0.02 to 0.40, wherein r 2 is 0.35 to 0.90 mm. In these embodiments, r 1 is not
- the mean skin foam density d 1 is defined as the mean density of foam in the skin portion extending from the surface to a depth of 12% of the foam thickness
- the mean core foam density d 2 is defined as the mean density of foam in the core portion extending from a depth of 40% of the foam thickness to a depth of 60% of the foam thickness.
- the mean skin foam density d 1 is obtained with the foam portion extending from the surface to a depth of 1.2 mm
- the mean core foam density d 2 is obtained with the foam portion extending from a depth of 4 mm to a depth of 6 mm.
- the mean foam densities d 1 and d 2 are obtained by cutting pieces of a given size from the skin and core portions of the foam and weighing the pieces.
- the ratio d 2 /d 1 of the mean core foam density d 2 to the mean skin foam density d 1 is preferably 0.2 to 0.8, more preferably 0 . 3 to 0 . 7 .
- the overall molded density of the urethane foam for shoe soles of the present invention is 0.15 to 0.50 g/cm 3 , preferably 0.20 to 0.40 g/cm 3 , more preferably 0.20 to 0.35 g/cm 3 , most preferably 0.20 to 0.32 g/cm 3 .
- the overall molded density is less than 0.15 g/cm 3 , the strength of the foam may become too weak for shoe sole application.
- the overall molded density exceeds 0.50 g/cm 3 , the entire foam becomes in the state of elastomer, thereby making it difficult to adjust the ratio of cell diameters.
- the overall molded density is 0.15 to 0.50 g/cm 3 , while the tensile strength is not less than 20 kg/cm 2 and more
- the overall molded density is 0.20 to 0.40 g/cm 3 while the tensile strength is not less than 20 kg/cm 2 . It is further more preferred that the overall molded density is 0.20 to 0.35 g/cm 3 , while the tensile strength is not less than 20 kg/cm 2 . It is still more preferred that the overall molded density is 0.20 to 0.32 g/cm 3 , while the tensile strength is not less than 24 kg/cm 2 .
- the tensile strength is determined one or more days after the molding when the tensile strength of a test sample has become stable. Incidentally, the tensile strength soon after demolding is preferably not less than 4 kg/cm 2 , more preferably not less than 6 kg/cm 2 .
- the mean skin foam density ( d 1 ) is 0.20 to 0.80 g/cm 3 , particularly 0.25 to 0.70 g/cm 3
- the mean core foam density (d 2 ) is 0.05 to 0.60 g/cm 3 , particularly 0.12 to 0.50 g/cm 3 .
- the cells be open cells.
- Any method can be used without limitation to prepare a urethane foam having a particular cell diameter and density for the present invention, and such a urethane foam can be obtained by optimizing molding conditions, such as mold temperature and mixer stirring rate, and choosing and controlling catalysts and/or foam stabilizers.
- foam stabilizers For example, as foam stabilizers, (A) a
- polyalkylsiloxane and (B) a polysiloxane-polyoxyalkylene copolymer may be combinedly used.
- invention include polydimethylsiloxanes and
- polymethylphenylsiloxanes with preference given to the polydimethylsiloxanes represented by formula (1) below.
- polydimethylsiloxane compounds represented by the formula those wherein X4 is 0 to 20 are particularly preferred.
- X4 is a number of 0 to 48.
- any foam stabilizer any foam stabilizer.
- polysiloxane-polyoxyalkylene copolymer can be used for the present invention, as long as it is normally used as a foam stabilizer for urethane foam production.
- polysiloxane-polyoxyalkylene copolymers include copolymers mainly comprising one or more polysiloxane components, such as polydimethylsiloxane and polymethylphenylsiloxane, and one or more polyoxyalkylene components, such as
- polyoxyethylene and polyoxypropylene are polyoxyethylene and polyoxypropylene.
- the components of such copolymers may be polymerized by block
- X2 is a number of 40 to 60; Y2 is a number of 5 to 15; m2 is a number of 4 to 10; and n2 is a number of 10 to 20.
- X3 is a number of 40 to 60; Y3 is a number of 5 to 10; m3 is a number of 5 to 15; and n3 is a number of 5 to 15.)
- the above-described polysiloxane-polyoxyalkylene copolymers are commercially and they can easily be
- polyalkylsiloxane (A) is preferably 0.02 to 1.00, more preferably 0.02 to 0.50.
- demold time tends to be extended, when it exceeds 1.00, the foam surface tends to become rough.
- the total amount of these foam stabilizers used is preferably 0.2 to 3.0 parts by weight, more preferably 0.5 to 2.0 parts by weight, based on 100 parts by weight of isocyanate-reactive compound. If the amount is less than 0.2 parts by weight, foam-stabilizing power for cell shape control is insufficient; if it exceeds 3.0 parts by weight, the foam strength tends to be decreased by plasticizing action.
- foam stabilizers as fluorine-based foam stabilizers and ordinary silicone- or fluorine-free surfactants may be optionally used.
- the amount of such foam stabilizer used is preferably 0.2 to 3.0 parts by weight based on 100 parts by weight of isocyanate-reactive compound. Mold temperature is normally 40 to 60°C.
- Isocyanate-reactive compounds which can be used for the present invention, i.e., compounds having at least two isocyanate-reactive hydrogen atoms in the molecule, include polyester polyols, polyether polyols and polymer polyols having a molecular weight of 400 to 10000, preferably 1000 to 3000.
- polyester polyols examples include condensation polymers formed between polyhydric alcohols, such as
- diethylene glycol diethylene glycol, neopentyl glycol and trimethylolpropane
- polybasic acids such as phthalic acid, maleic acid, malonic acid, succinic acid, adipic acid and terephthalic acid, and having a hydroxyl group at its terminus.
- Useful polyether polyols include polyether polyols and polytetramethylene ether glycols obtained by addition polymerization of alkylene oxides to polyhydric alcohols, such as ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, glycerol,
- a polyhydroxy compound having a molecular weight of not less than 32 and less than 400 may be used as an ordinary chain extender and crosslinking agent according to necessity.
- the properties of the polyurethane foam for shoe soles obtained can optionally be changed.
- polyisocyanates for the present invention examples include tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate,
- the prepolymers are polymers having active isocyanate groups at its ends prepared by previously reacting an excess of polyisocyanate with polyols such as polyester polyol and polyether polyol.
- the prepolymers are used as a precursor for the production of a polyurethane.
- the amount of polyisocyanate used is normally 50 to 150 parts by weight, preferably 60 to 140 parts by weight based on 100 parts by weight of isocyanate-reactive compound.
- a blowing agent is used in producing a urethane foam for shoe soles.
- the preferred blowing agent for the present invention is water, which generates carbon dioxide upon reaction with polyisocyanate.
- the amount of water used be 0.4 to 2.0 parts by weight, more preferably 0.8 to 1.8 parts by weight, based on 100 parts by weight of
- Any catalyst can be used for the present invention, as long as it is normally used as a catalyst for urethane foam production.
- amine catalysts such as
- triethylenediamine, and 1,2-dimethylimidazole are preferably used, and 1,2-dimethylimidazole and an amine catalyst may be used in combination.
- the amount of catalyst used is
- components such as anti-discoloration agents, stabilizers, and antifungal agents may be optionally used in the present invention.
- a urethane foam is prepared by a known one-shot method utilizing a prepolymer or a semi-prepolymer.
- the reaction mixture is injected into a mold.
- suitable mold materials include metals, such as aluminum, and plastic materials, such as epoxy resin.
- the expandable reaction mixture forms a foam in the mold. Blowing in the mold is conducted so that the
- resulting foam has a cell structure on the surface thereof, and may also be conducted so that the foam has a
- the present invention allows the expandable reaction mixture to be introduced into the mold in an amount such that the resulting foam just fills the mold.
- the expandable reaction mixture can also be introduced into the mold in an amount exceeding the minimum amount required to fill the mold with the resulting foam.
- any known silicone-based release agent is used to ensure desired blowing in the mold.
- reaction mixture was then added drop by drop, while the reaction temperature was kept at 85 to 100°C. Then, reaction was carried out at 100 to 105°C for 5 hours. The reaction mixture was then
- copolymer having a molecular weight of about 50000 and represented by the formula:
- polyester polyols used ethyleneglycol- diethyleneglycol adipate
- OHV Hydroxyl Value
- foam stabilizers used were a polyalkylsiloxane mixture
- the molding conditions used are as follows:
- Polyol mixture and prepolymer retention temperature 40 ⁇ 2°C
- the urethane foam obtained in each example was evaluated as follows:
- the mean cell diameters r 1 and r 2 are obtained by taking a cross-sectional photomicrograph of the urethane foam using a scanning electron microscope (SEM), and calculating number (arithmetic) average diameters using the value of maximum diameter in a given direction (also referred to as Krummbein diameter as described in
- Split tear value was determined in accordance with the method of ASTM D-3574. Specifically, a 25.4 x 150 x 10 mm test piece was cut out from a 200 x 150 x 10 mm sheet and horizontally cut over a distance of 50 mm at a 5 mm depth from the surface (see Figure 1). Using the autograph
- the split tear value was determined at a speed of 50 mm/min, and the actual measurement was divided by 2.54 to obtain the split tear value.
- Moldability was evaluated by visually assessing the sheet surface voids, skin condition, bubble size, shrinkage, etc., using a 3-grade rating system: good (o), single defect ( ⁇ ), and two or more defects (x). The results obtained are shown in Tables 3 and 4.
- the starting components for preparing a polyurethane foam were mixed according to the formulas shown in Table 2.
- the foam stabilizers used were commercially available side chain EO• PO modified silicone (Comparative Example 1) and the EO• PO linear block modified silicone obtained in
- Synthesis Example (Comparative Example 2), and each of the stabilizers above was used singly.
- the prepolymer used was EDDYFOAM B-2009 (manufactured by Kao Corporation), which was the same kind as that used in the above Examples.
- the urethane foam for shoe soles of the present invention has good moldability and a high split tear value.
- the urethane foam obtained in Comparative Example 1 having an r 1 /r 2 ratio exceeding 0.80 and a low r 2 value, had poor moldability and a low split tear value for the molded density.
- the urethane foam obtained in Comparative Example 2 having an r 1 /r 2 ratio lower than 0.02, had poor moldability.
- a polyurethane foam was prepared by mixing the starting components according to the formulas in Table 5.
- the above mentioned EDDYFOAM B-2009 was used as prepolymer.
- a polyurethane foam was prepared under the same conditions as in Examples 1 to 15 according to the formulas shown in Table 7 .
- the same foam stabilizer as that used in Examples 1 to 15 was used.
- a polyurethane foam was prepared according to the formulas shown in Table 7.
- the foam stabilizer used was the side chain EO• PO modified silicone.
- the prepolymer used was EDDYFOAM B-6106M manufactured by Kao Corporation, which was the same prepolymer as used in Examples 18 to 21.
- the urethane foam for shoe soles of the present invention has a good moldability and a high split tear value.
- the urethane foam obtained in Comparative Examples 3 and 4 having an r 2 /r 2 ratio exceeding 0.80, had a low split tear value.
- the starting components were mixed according to the formulas in Table 9 to yield a 200 x 150 x 10 mm polyurethane foam sheet.
- the molding conditions used are as follows:
- Polyol mixture and prepolymer retention temperature 40 ⁇ 2°C
- foam stabilizer A is a mixture of polyalkylsiloxanes represented by the following formula:
- foam stabilizer B is a copolymer prepared in Synthesis Example.
- the urethane foam for shoe soles obtained by the present invention has a good moldability. Also, the tensile strength soon after demolding is large.
- a polyurethane foam with a good moldability can be obtained with maintaining a high split tear strength.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Applications Claiming Priority (11)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7829496 | 1996-03-05 | ||
| JP78293/96 | 1996-03-05 | ||
| JP7829396 | 1996-03-05 | ||
| JP78294/96 | 1996-03-05 | ||
| JP7829496 | 1996-03-05 | ||
| JP8485096 | 1996-03-12 | ||
| JP84850/96 | 1996-03-12 | ||
| JP8484996 | 1996-03-12 | ||
| JP8484996 | 1996-03-12 | ||
| JP84849/96 | 1996-03-12 | ||
| PCT/JP1997/000632 WO1997032923A1 (en) | 1996-03-05 | 1997-02-28 | Urethane foam for shoe soles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0885256A1 true EP0885256A1 (de) | 1998-12-23 |
| EP0885256B1 EP0885256B1 (de) | 2000-06-07 |
Family
ID=27466155
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP19970905431 Expired - Lifetime EP0885256B1 (de) | 1996-03-05 | 1997-02-28 | Urethanschaum für schuhsohlen |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US6099955A (de) |
| EP (1) | EP0885256B1 (de) |
| CN (1) | CN1065884C (de) |
| ID (1) | ID16099A (de) |
| WO (1) | WO1997032923A1 (de) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2844799B1 (fr) * | 2002-09-19 | 2004-11-19 | Crompton Corp | Procede pour ameliorer la resistance a l'hydrolyse d'un elastomere d'urethanne, polyester polyol pour sa mise en oeuvre, elastomere obtenu et son utilisation |
| CN101061155B (zh) * | 2004-11-24 | 2010-07-21 | 旭硝子株式会社 | 软质聚氨酯泡沫塑料、其制造方法以及汽车用座垫 |
| ITMI20052257A1 (it) | 2005-11-25 | 2007-05-26 | Basf Ag | Suole intermedie per scarpe dio sicurezza da espanso poliuretano di bassa densita' |
| CN101486801B (zh) * | 2008-12-30 | 2012-05-30 | 浙江华峰新材料股份有限公司 | 添加热发泡性微球的低密度聚氨酯微孔弹性体及其制备方法 |
| CN101628964B (zh) * | 2009-08-17 | 2011-09-07 | 旭川化学(苏州)有限公司 | 用于制作聚氨酯鞋底材料的双组份 |
| JP5798656B1 (ja) * | 2014-03-26 | 2015-10-21 | 住友理工株式会社 | ウレタン製バンパスプリングおよびその製法 |
| JPWO2021130903A1 (de) | 2019-12-25 | 2021-07-01 | ||
| JP7243941B2 (ja) * | 2021-04-13 | 2023-03-22 | Dic株式会社 | 積層体及び靴底 |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU8900182A (en) * | 1981-08-10 | 1983-02-22 | Whitney & Co., Inc. | Molding of unsaturated polyester |
| JPS61258822A (ja) * | 1985-05-13 | 1986-11-17 | Inoue Mtp Co Ltd | タ−ル含有ポリウレタンフオ−ム成形品 |
| US5126181A (en) * | 1991-09-23 | 1992-06-30 | E. I. Du Pont De Nemours And Company | Microporous discs of elastic segmented polyurethane |
| EP0559216A1 (de) * | 1992-03-06 | 1993-09-08 | Tosoh Corporation | Verfahren zur Herstellung von Aussenkantschichten hoher Dichte aufweisenden Urethan-Schaumstoffen |
-
1997
- 1997-02-28 ID ID970611A patent/ID16099A/id unknown
- 1997-02-28 US US09/142,231 patent/US6099955A/en not_active Expired - Lifetime
- 1997-02-28 EP EP19970905431 patent/EP0885256B1/de not_active Expired - Lifetime
- 1997-02-28 WO PCT/JP1997/000632 patent/WO1997032923A1/en not_active Ceased
- 1997-02-28 CN CN97192808A patent/CN1065884C/zh not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
|---|
| See references of WO9732923A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1212715A (zh) | 1999-03-31 |
| WO1997032923A1 (en) | 1997-09-12 |
| CN1065884C (zh) | 2001-05-16 |
| ID16099A (id) | 1997-09-04 |
| EP0885256B1 (de) | 2000-06-07 |
| US6099955A (en) | 2000-08-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8178591B2 (en) | Carbon dioxide blown low density, flexible microcellular polyurethane elastomers | |
| KR100206399B1 (ko) | 연질 세그먼트 이소시아네이트 말단기를 갖는 예비중합체로부터 폴리우레탄 탄성중합체를 제조하는 방법 | |
| CA2367077C (en) | Carbon dioxide blown low density, flexible microcellular elastomers suitable for preparing shoe components | |
| EP1124875B1 (de) | Verfahren zum herstellen von mikrozellulären polyurethanelastomeren | |
| US6022903A (en) | Permanent gas blown microcellular polyurethane elastomers | |
| PT897402E (pt) | Processo de fabrico de corpos moldados elasticos em poliuretano com uma superficie compacta e um nucleo celular | |
| US3901959A (en) | Polymeric materials | |
| CZ270794A3 (en) | Process for preparing foamy polyurthane shaped parts without use of fluorochlorinated hydrocarbons | |
| KR970021119A (ko) | 이소시아네이트-종결된 초기 중합체를 사용한 밀도가 매우 낮은 성형폴리우레탄 발포체 | |
| EP0885256B1 (de) | Urethanschaum für schuhsohlen | |
| PL169691B1 (pl) | Sposób wytwarzania polimeru poliuretanowego PL PL PL PL PL PL PL | |
| JP2025094119A (ja) | 硬度勾配を有する軟質ポリウレタンフォームの製造法 | |
| JP3093988B2 (ja) | 靴底用ウレタンフォーム | |
| JP4718157B2 (ja) | 軟質ポリウレタン発泡体、軟質ポリウレタン発泡体の製造方法、及びクッション | |
| JP5571905B2 (ja) | ポリウレタン発泡成形体 | |
| AU655315B2 (en) | Polyurethanes having improved physical properties | |
| JP3942745B2 (ja) | ポリウレタンフォームの製造法 | |
| JP3269609B2 (ja) | ポリウレタンフォームの製造法 | |
| DE69702244T2 (de) | Urethanschaum für schuhsohlen | |
| US8138235B2 (en) | Polyurethane foam and method for manufacturing the same | |
| JP3926195B2 (ja) | ポリウレタンフォーム | |
| JP3477290B2 (ja) | ポリウレタンフォームの製造方法 | |
| JPH0680106B2 (ja) | ポリウレタンフォームの製造方法 | |
| JP2006131717A (ja) | ポリウレタン発泡体 | |
| MXPA06005972A (en) | Carbon dioxide blown low density, flexible microcellular polyurethane elastomers |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| 17P | Request for examination filed |
Effective date: 19980902 |
|
| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): DE FR GB |
|
| GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
| GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
| GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
| 17Q | First examination report despatched |
Effective date: 19990311 |
|
| GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
| AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): DE FR GB |
|
| REF | Corresponds to: |
Ref document number: 69702244 Country of ref document: DE Date of ref document: 20000713 |
|
| ET | Fr: translation filed | ||
| PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
| 26N | No opposition filed | ||
| REG | Reference to a national code |
Ref country code: GB Ref legal event code: IF02 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20110218 Year of fee payment: 15 Ref country code: DE Payment date: 20110223 Year of fee payment: 15 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20110223 Year of fee payment: 15 |
|
| GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20120228 |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20121031 |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 69702244 Country of ref document: DE Effective date: 20120901 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20120229 Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20120228 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20120901 |